Kokaku, Yu-ichi
(Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan)
,
Hatano, Yoshihiko
(Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan)
,
Shimamori, Hiroshi
(Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan)
,
Fessenden, Richard W.
(Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan)
Thermal electron attachment of O2 in O2-C2H4, O2-CO2, and O2-neopentane mixtures has been investigated at room temperature, using a microwave conductivity technique combined with pulse radiolysis. The measurements have been extended to a higher pressure region (∼850 Torr) than previous observati...
Thermal electron attachment of O2 in O2-C2H4, O2-CO2, and O2-neopentane mixtures has been investigated at room temperature, using a microwave conductivity technique combined with pulse radiolysis. The measurements have been extended to a higher pressure region (∼850 Torr) than previous observations in order to compare them with the results of an electron swarm method at very high pressures. From low pressure data, the values of (2.0±0.3) ×10−30, (3.2±0.3) ×10−30, and (7±1) ×10−30 cm6/molecule2 sec are determined for the overall three body attachment rate constants of O2 with the stabilizing partners C2H4, CO2, and neopentane, respectively. In each case, the effective rate constant continued to increase with increased density and exceeded those predicted by the Bloch-Bradbury mechanism by sizeable amounts. The excess attachment is suggested to involve pre-existing van der Waals complexes such as (O2⋅C2H4). Some quantitative conclusions which follow from this mechanism are given.
Thermal electron attachment of O2 in O2-C2H4, O2-CO2, and O2-neopentane mixtures has been investigated at room temperature, using a microwave conductivity technique combined with pulse radiolysis. The measurements have been extended to a higher pressure region (∼850 Torr) than previous observations in order to compare them with the results of an electron swarm method at very high pressures. From low pressure data, the values of (2.0±0.3) ×10−30, (3.2±0.3) ×10−30, and (7±1) ×10−30 cm6/molecule2 sec are determined for the overall three body attachment rate constants of O2 with the stabilizing partners C2H4, CO2, and neopentane, respectively. In each case, the effective rate constant continued to increase with increased density and exceeded those predicted by the Bloch-Bradbury mechanism by sizeable amounts. The excess attachment is suggested to involve pre-existing van der Waals complexes such as (O2⋅C2H4). Some quantitative conclusions which follow from this mechanism are given.
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